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Advanced treatment of textile wastewater for reuse using

electrochemical oxidation and membrane filtration

Xuejun Chen1, Zhemin Shen1*, Xiaolong Zhu2, Yaobo Fan2, Wenhua Wang1
School of Environmental Science and Engineering, Shanghai Jiaotong University, Dongchuan Road 800, Shanghai, 200240,
PR China
Research Center for Eco-environmental Sciences, Chinese Academy of Sciences, Shuangqing Road 18, Beijing 10085, PR China


The treatment of textile wastewater for reuse using an electrochemical oxidation step combined with a membrane filtration
step is reported in this paper. The electrolytical process is a traditional one, which is easy to scale up and to apply in practice.
This paper proposes a modification of the transfer-flow membrane (TFM) module with fibres welded in an arc-shape to
enhance the mechanical properties of the fibres and to increase the specific membrane surface of TFM modules. The goal
of this research was to study the performance of the arc-shaped TFM module to demonstrate these sequences of
electrochemical oxidation coupled with membrane filtration processes and to develop a potential dyehouse wastewater
treatment system for reuse. Two testing sequences of electrochemical oxidation and membrane filtration were studied in
a sequential batch order. The results show clearly that fibres welded in an arc-shape can enhance the mechanical properties
of the fibres effectively and that electrochemical oxidation and membrane filtration as sequential processes are feasible.
Electrochemical oxidation has a high removal (89.8% efficiency) of the chemical oxygen demand (COD) of the wastewater
while the membrane filter can almost totally remove the total suspended solids (TSS) (nearly 100% reduction) and turbidity
(98.3% elimination) in it. Coincidentally, their advantages make up for their disadvantages. After these two steps, all the
wastewater indices decrease to low levels; in particular, COD levels are reduced to 18.2 mg·l-1. The treated water can be
reused in many production areas of the textile dyehouse factory. To take best advantage of this disposal system, the two
processes should run in a rational sequence, with membrane filtration following the electrochemical oxidation process. With
widely studied electrodes, this research offers a promising way for recycling textile wastewater.

Keywords: electrolysis, oxidation, membrane, dye, wastewater treatment

Introduction wastewaters bearing high loads of organic compounds, especially

some bio-refractory organic pollutants. Such treatment produces
Increasingly stringent effluent discharge permit limitations have total degradation of compounds to CO2 and H2O or at least a
been put into effect (Defazio and Lemley, 1999). The textile considerable decrease in toxicity. A direct anodic process or an
industry generally has difficulty in meeting wastewater discharge indirect anodic oxidation via the production of oxidants such as
limits, particularly with regard to dissolved solids, ionic salts, pH, hydroxyl radicals, ozone, etc. usually destroys the organic and toxic
COD, colour, and sometimes, heavy metals (Author: This is a pollutants present in wastewater such as dyes and phenols. Tita-
consulting firm and the name has to be written out in full: Steffen, nium electrodes covered with very thin layers of electrodeposited
Robertson and Kirsten, 1993; Lin and Peng, 1996; Vlyssides et al., noble metals have recently been used for electro-oxidation. Elec-
1999) trodes can also be coated with ruthenium, rhodium, lead and stannum
The problem of colour in textile dyehouse effluent and the oxide (Vlyssides and Israilides, 1998; Chen et al., 2003; Taghizadeh
possible problems associated with the discharge of dyes and dye et al., 2000). By means of electrochemical oxidation, pollutants in
degradation products are of concern. Traditional methods for wastewater can be completely mineralised by electrolysis using high
dealing with this kind of wastewater are usually the biological, oxygen over-voltage anodes such as PbO2 and boron-doped dia-
physical and chemical techniques as well as the various combina- mond. (Nicola and Badea, 1996; Tezuka and Jwasaki, 1996; Casado
tions of theses. It has been widely reported that many dye chemicals and Brillas, 1996). Naohide et al. (1998) treated dyestuff using PbO2
are difficult to degrade using conventional biological treatment anode. In their study, Orange II was decolourised completely by a
processes. It is more important to reuse this kind of wastewater than 120 min electrolysis procedure using a PbO2 anode at current
to discharge it after treatment in that the costs of chemicals, energy density of 0.2 A cm-2. Polcaro et al. (1999) studied the performance
and water continually increase. of the Ti/PbO2 anode during electrolysis of 2-cholorophenol in
Many advanced treatments have been studied and electrochemical terms of faradic yield and fraction of toxic intermediates removed.
oxidation has been applied to many kinds of wastewater (Naumczyk Ti/PbO2 anode was used as the anode in this experiment, since it has
et al., 1996; Simonsson, 1997). It is presented as an effective, been widely studied and used in some electrolysis industries, such
selective, economical, and clean alternative for dealing with as chlorine producing factories.
Membrane systems have also been reported in dyehouse
* To whom all correspondence should be addressed. wastewater treatment (Jadwiga et al., 1998; Wu et al., 1998 and
+86-21-54745262; fax: +86-21-54742863; Grimm et al., 1998). Membrane systems can successfully remove
e-mail: the large amount of suspended solids (SS) in wastewater. The aim
Received 10 March 2004; accepted in revised form 27 September 2004. of introducing membrane filtration is not only to reduce water

Available on website ISSN 0378-4738 = Water SA Vol. 31 No. 1 January 2005 127
Arc-shaped transfer-flow membrane
module specifications and operating

Manufacturer Centres of Zhongke


Membrane material PAN

Weight cut-off 500.00
Outer diameter 1 mm
Figure 1 Length 16 cm
Transfer-flow membrane module with fibre welded The total membrane area 0.23 m2
in an arc-shape
Suction pressure 0.03 MPa
Circulating flux 40 l·h-1
consumption and wastewater effluents, but also to reduce the
Aeration rate 0.2 m3·h-1
consumption of energy as the warm water can be recovered.
Crossflow filtration was one of the most important methods
proposed to overcome concentration polarisation and membrane
fouling. Different from classical dead-end filtration, the suspension TABLE 2
flow in crossflow microfiltration system is tangential to the filter Characteristics of
surface and the wall with a velocity ranging from 1 to 4 m·s-1 in order wastewater used
to control and limit the development of the coating on the membrane
(Bailey et al., 1994). In addition to the ratio of circulating wastewater Character Value
to permeate flux being as high as 10~20:1, its power consumption
of water treatment varies between 5 kWh·m-3 and 8 kWh·m-3 (Van pH 7.2
Dijk and Ronken, 1997; Kim et al., 2002). COD, mg·l-1 178.5
To lessen fibre contamination and polarity, Triqua (Knops et Turbidity, NTU 18.5
al., 1992) first researched a new type of membrane separator, the TSS (mg·l-1) 285
TFM separator. Influent flow is not parallel to the axis of the module ADMI colour unit 1 520
as it is in crossflow membrane, but perpendicular to the fibre. It
strengthens mass transfer in boundary layer, resulting in the fibres filtration process for the treatment and reuse of textile dyehouse
themselves serving as turbulence promoters. High-feed flow veloci- wastewater. The goal of this research is to study the performance
ties or auxiliary turbulence promoters are not necessary. Therefore, of the arc-shaped transfer-flow membrane module, at the same time,
compared with crossflow modules, transverse flow modules require to demonstrate these processes and to develop a potential dye-
less membrane area and consume less energy to produce a given wastewater treatment system for reuse.
amount of permeate. Energy requirements for this type of mem-
brane filtration are about 0.1 to 0.5 kWh·m-3 (Van Dijk and Ronken, Materials and methods
However, the end-fibres tend to leak with sustained high stress Electrode preparation
caused by recycling wastewater (Sakellariou, 1998; Zhang, 2000).
To overcome these shortcomings, a modification of the transfer- A titanium plate (8cm×3cm) was galvanized with PbO2. A Ti/PbO2
flow membrane module with the fibre welded in an arc-shape to plate was used as an anode while stainless steel meshwork of the
enhance the mechanical properties of the fibres and to increase the same dimensions served as a cathode in this system.
specific membrane surface of TFM modules is proposed in this
paper. This type of fibre arrangement can efficiently decrease the Membrane filter
stress of the end-fibres and make the membrane tough, highly
tenacious and strongly resistant to bending fatigue. This arc-shaped Figure 1 shows the transfer-flow membrane module with the arc-
fibre is longer than a linear fibre in the same scale module, which shaped welded fibre. Its specifications and operating conditions are
increases the specific membrane surface of TFM modules to more given in Table 1. The dimension of the arc-shaped transfer-flow
than that of the normal transfer-flow membrane module. membrane module is 150 × 150 × 100 mm3.
Membrane-wet oxidation, an integrated process, has been
demonstrated by Dhale and Mahajani (2000) to treat the disperse Materials
dye bath waste. Li and Zhao (1999) have developed an advanced
treatment process for dyestuff wastewater treatment. A TiO2 The wastewater sample used was collected after a bio-filter treat-
photo-catalytic reactor ran as advanced treatment for complete ment from a textile dyehouse in Beijing. It looked red. The compo-
decolourisation and high COD removal. Suspended TiO2 powder sition of the sample is shown in Table 2.
used in photo-oxidation was separated from the slurry by a
membrane filter and treated wastewater was continuously recycled Instrumentation
to the photo-reactor.
However, as yet, there has not been a method employing the Solution pH values were detected by a pH/mV meter (COLE
electrochemical oxidation process combined with the membrane PARMER, USA). Samples’ colour was analysed by U-3010

128 ISSN 0378-4738 = Water SA Vol. Vol. 31 No. 1 January 2005 Available on website
Anode DC
Graphite Membrane
Water position
Figure 2 sensor
diagram of
electrochemical Cleaning water
Input Output
oxidation pond

Water position Anti-rinsing pump

Input Recycling
pump pump Anti-rinsing

Spectrophotometer (Hitachi, Japan). Each dye solution was scanned

and its maximum absorbency visible wavelength was detected. The TABLE 3
colour unit was detected by a standard method (Author: specify and Treatment effect of electrochemical oxidation as a
refer to the method) COD and the colour remains ratio was calculated first step
as follows:
Character 30 min 50 min
Remains colour % =ABS/ ABS0 ×100% (1)
(ABS0: ABS value before electrolysis) Value Remains/% Value Remains/%

(ABS: ABS value after electrolysis)

Remains COD % = COD/ COD0 ×100% (2) pH 7.0 6.9
(COD0: COD value before electrolysis) COD, mg·l-1 78.6 44.0 46.0 25.8
(COD: COD value after electrolysis) Turbidity, NTU 9.8 53 8.7 47
TSS (mg·l-1) 260 91.2 245 86
Methods ADMI colour units 395 26.0 145 9.5

Electrochemical oxidation of wastewater was conducted in an

undivided reactor of 1.2dm3 volume. The overall experimental set- TABLE 4
up mainly consists of a cell unit, water position control system, a Treatment results of membrane filtration
set of recycling system and a membrane unit, as shown in the as a second step
following Fig. 2. Electrolysis was conducted at 8V DC and electric
current density was kept at 124 A·m-2. After electrolysis, CODCr Character Value Remains /%
and the colour of the solution are determined by a U-3010 Spectro-
photometer, respectively. pH 7.6
COD, mg·l-1 18.2 10.2
Results and discussion Turbidity, NTU 0.32 1.7
TSS (mg·l-1) 0 0
Electrochemical oxidation process prior to membrane ADMI colour units 135 8.9
filtration process

To test these processes, the two processes were run in sequential wastewater treatment. After the two steps, the COD remains at a
batch order. Firstly, electrochemical oxidation was performed in a low level, only 18.2 mg·l-1, and so do other indices. The treated water
cubic reactor and followed by a membrane filtration process. The can be reused in many production areas of the textile dyehouse
results of the former step are given in Table 3. It is seen from the table factory. It is reported that Ti/RuO2, Ti/SnO2 and Ti/SnO2+Sb2O5
that electrochemical oxidation can more efficiently remove colour electrodes have better ability to oxidize toxic compounds and are
than turbidity and SS. The remaining ratio of colour is 145: 1 520 more efficient than our Ti/PbO2 anode. If these more efficient
(9.5%), which is less than the TSS ratio. The reason is that it is electrodes are used in this system, the wastewater can be treated
difficult for the oxidative radicals, ·O2 or HO· to break the large more effectively, and can be used in all production areas of the textile
amount of solids particles in the sample. factory. It can therefore be deduced that this system provides a
Table 4 shows that the second step can make up the deficiency promising way to treat textile dyehouse wastewater for reuse.
of the first one. Membrane filtration can remove almost all the TSS The wavelength scan result in Fig. 3 confirms the above
and the turbidity, which is difficult for a chemical oxidation system conclusion. After both steps, the absorption among visible wave-
to achieve. These two processes work well together for textile length scope is decreased to a low level.

Available on website ISSN 0378-4738 = Water SA Vol. 31 No. 1 January 2005 129
W a v e le n g t h S c a n W a v e le n g t h S c a n
A bs A b s
0 .1 5
0 .1 0
0 .0 9
0 .0 8
0 .0 7 0 .1 0
0 .0 6
0 .0 5
0 .0 4 0 .0 5
0 .0 3
0 .0 2
0 .0 1
0 .0 0 4 0 0 5 0 0 6 0 0 7 0 0 8 0 0
400 500 600 700 800

W a v e le n g t h S c a n
A bs
W a v e le n g t h S c a n 0 .1 5
A b s
0 .1 5 0 .1 4
0 .1 3
0 .1 2
0 .1 1
0 .1 0
0 .1 0 0 .0 9
0 .0 8
0 .0 7
0 .0 6
0 .0 5
0 .0 5 0 .0 4
0 .0 3
0 .0 2
0 .0 1
0 .0 0 400 500 600 700 800
4 0 0 5 00 6 00 70 0 80 0

W a v e le n g t h S c a n
W a v e le n g t h S c a n A bs
A bs 0 .1 5
0 .1 4
0 .1 0 0 .1 3
0 .0 9 0 .1 2
0 .0 8 0 .1 1
0 .1 0
0 .0 7 0 .0 9
0 .0 6 0 .0 8
0 .0 5 0 .0 7
0 .0 4
0 .0 6
0 .0 5
0 .0 3 0 .0 4
0 .0 2 0 .0 3
0 .0 1 0 .0 2
0 .0 1
0 .0 0
nm nm
400 500 600 700 800 400 500 600 700 800

Figure 3 Figure 4
Wavelength scan of textile wastewater of raw sample (upper), Wavelength scan of textile wastewater of raw sample (upper),
sample after electrochemical oxidation as a first step (middle) sample after membrane filtration as a first step (middle) and
and sample after both the two steps (lower) sample after both the two steps (lower)

Membrane filtration process prior to electrochemical

TABLE 5 oxidation process
Treatment results of membrane filtration
as a first step Secondly, another order of the two processes was also performed.
Electrochemical oxidation was conducted after membrane filtration.
Character Value Remains /% Table 5 and Table 6 show the experimental results of this testing
sequence. The advantages and disadvantages of membrane filtration
pH 7.1 are indicated in Table 5. Its poor decolourisation effect must be
COD, mg·l-1 67.4 37.8 because most the dyestuffs are small molecules. In general, the
Turbidity, NTU 0.40 2.2 smaller the size of a molecule, the higher the passing rate through the
TSS (mg·l-1) 0 0 membrane. Figure 3 gives the absorption states in this experimental
ADMI colour units 942 62 order and shows that most of the colour is disposed of in the second
However, even after being treated by a second electrochemical
oxidation process, the colour unit of the solution is no less than 500
TABLE 6 in the latter test order and the COD removal is not as effective as
Treatment effect of electrochemical in the previous experiment. This may be attributed to lower SS in
oxidation as a second step the wastewater after the filtration. Some particles in the solution
may serve as catalyst, accompanied by many kinds of ions. Many
Character Value Remains /% form-changeable ions, such as Ag2ÿ0Co3ÿ and Fe3ÿ, can be oxidative
intermediates and accelerate the degradation of organic pollutants.
pH 7.1 The function of these ions has been confirmed in the oxidation of
COD, mg·l-1 24.7 13.8 benzene, phenol and oil.
Turbidity, NTU 0.9 4.9 By contrast, the change in sequence of these two steps leads to
TSS (mg·l-1) — — a variation in the result. Author to check The former method with
ADMI colour units 225 14.8 electrochemical oxidation being the first step is prior to the latter one.
In order to make full use of this disposal system, it is important that
the two processes should run in a rational sequence.

130 ISSN 0378-4738 = Water SA Vol. Vol. 31 No. 1 January 2005 Available on website
100 Conclusions
90 di r ect el ect r ol ysi s
el ect r ol ysi s af t er f i l t r at i on Transfer-flow membrane modules with arc-shaped welded fibres

can enhance the mechanical properties of the fibres and increase the
specific membrane surface of TFM modules. The phenomenon of
40 fibres leaking did not occur during the experiment. Two testing
30 sequences of electrochemical oxidation and membrane filtration
20 were studied. The two processes treated textile dyehouse wastewater
10 samples in turn. The results clearly show the feasibility of these two
0 sequential processes. Electrochemical oxidation effectively removes
0 10 20 30 40 50 60 the colour of the wastewater while the membrane filter almost
Ti me/ mi n totally removes the TSS in it. It is obvious that their advantages can
Figure 5 make up for the disadvantages of each. After both steps, all the
Colour removal of wastewater with the time, at 8V D.C.,
wastewater indices decrease to low levels. The treated water can be
electric current density 124 mA cm-2
reused in many production areas of the factory. To make the most
of this disposal system, it is important that the two processes
2.5 should run in a rational sequence. It is indicated that the membrane
filtration process should follow the electrochemical oxidation proc-
2 ess. As electrolysis is a traditional method, it is easy to operate an
electrochemical oxidation process and to apply it. With more
efficient electrode materials, this system will provide us with a more
1 effective method for recycling textile dyehouse wastewater.

0.5 Acknowledgements
nm This work was supported financially by the Chinese National
200 300 400 500 600 700 800
Natural Science foundation (20377028) and the open foundation of
State Key Laboratory of Environmental Aquatic Chemistry. The
Figure 6 authors are also grateful to anonymous reviewers for their valuable
Spectrum of wastewater extraction by CH2Cl2 before treatment comments and suggestions.

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